Imparting crease recovery properties to cellulose with precursors of butadiene diepoxide



United States Patent IMPARTING GREASE RECOVERY PROPERTIES TO CELLULUSE WITH PRECURSORS 0F BUTADI- ENE DIEPOXIDE John B. McKelvey, Ralph J. Berni, and Ruth R. Benerito, New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture N0 Drawing. Filed Jan. 7, 1963, Ser. No. 249,959 6 Claims. (Cl. 8-120) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to cellulose ethers. More particularly, this invention relates to the production of 2,3 dihydroxybutyl-l,4 diethers of cellulose.

A primary object of the present invention is to provide a process for the etherification of hydroxyl group con- .taining cellulose textile fibers with d,l or meso 1,4 dihydroxy-2,3 dibromo (or dichloro) butane, or with 1,4 dihalo-2,3 dihydroxy butane, without destroying the textile properties of the fiber. A further object is to provide a process of modifying the properties of cellulosic textiles that contain hydroxyl groups, to impart or enhance properties such as wet and dry wrinkle recovery. An other object is to provide 2,3 dihydroxy butyl-l,4 diethers of cellulose in textile fiber form wherein the etherification treatment is durable to repeated home and commercial launderings. A further object is to provide partially etherified cellulosic materials by using precursors of butadiene diepoxide, which is an excellent crosslinking agent for cellulosic materials; however, butadiene diepoxide is more expensive to make than its precursors, and is toxic and volatile, which add further to the cost of handling.

The application of butadiene diepoxide to cellulosic materials .to obtain improved wet and dry wrinkle recovery is known in prior art. However, no mention of the use of precursors of butadiene diepoxide has been found, and it is assumed that prior attempts to attain improvement in wet and dry crease recovery of cellulosic materials using 2,3-dihydroxy-1,4 d-ibromo (or dichloro) butane were unsuccessful or untried.

Due to the reported toxicity in handling butadiene diepoxide, it was decided to start with the precursors of this compound so that the epoxide could be generated in situ in the cellulosic material in the presence of sodium hydroxide (dehydrohalogenation). Unfortunately, dehydrohalogenation in an all aqueous medium leads to solubiliza-tion and/ or hydrolysis of the reaction products and no reaction with cotton cellulose, as judged by the absence of weight gains after reaction with the etherifying agents.

In general, in accordance with the present invention, cellulosic material containing hydroxyl groups is etherified by reacting it with an etherifying agent of a halohydrin of butane, wherein the 2,3-hydroxybutyl radical contains four carbon atoms. In carrying out the etherifying process of the invention, the etherification is accomplished by a reaction between the cellulosic material and one or more 2,3 dihydroxy-IA dihalobut-ane, or 1,4 dihydroxy- 2,3 dihalobutane etherifying agents in the presence of ethanolic solutions of sodium hydroxide for dehydrohalogenation and production of butadiene diepoxide in situ during the reaction process. When the precursor is applied from aqueous solution the process of the present invention is characterize-d by a critical sequence of addition of the reactants, drying, adding alcoholic base, curing, and washing the etherified cellulosic material, which sequences are described below. When absolute alcohol is the solvent a one step process can be used as shown.

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Substantially any cellulosic material containing hydroxyl groups can suitably be employed in the present process. Illustrative examples of such material include cellulose derived from cotton, flax, ramie, and the like vegetable materials; wood cellulose, regenerated cellulose such as viscose rayon, and the like; partial esters of cellulose such as partially acetylated cellulose, beta-propiolactone reacted cellulose, and the like; partial ethers of cellulose such as partially cyanoethylated, partially aminoethylated, partially carboxymethylated and the like partially etheriiied cellulose materials. In general, the cellulosic textile fibers, in the form of free fibers, silvers, yarns, threads, or fabric including the natural fibers and partial ethers or partial esters thereof, which are produced by reactions in which the fibers retain their cellulosic textile properties, are preferred starting materials. The cellu losic textile fibers in the form of spun textiles, i.e., yarns, threads or cloths, are particularly suitable starting materials.

In reacting the cellulosic material with the etherifying agent-the dihalohydrins of butanesubstantially any apparatus usually employed in the etherification of cellulose can be employed. In carrying out the preferred etherifi cation process, the 'cellulosic material to be reacted i-s padded twice with an aqueous solution of the etheri-fying agent in concentrations varying from 5% to 20%. The tabric is then dried in a forced-draft oven before padding with from 3% to 10% ethanolic or methanolic sodium hydroxide. The fabric is then cured for approximately 16 hours in a polyethylene bag at 25 C., or for short intervals in a forced-draft oven at temperatures ranging from 100 to 125 C.

The application of these halohydrins may be done separately or mixed in the same bath with methanolic or ethanolic sodium hydroxide solutions, then applied to the cellulosic materials, to obtain textiles with relatively similar desired characteristics.

Following completion of the et-herifying reaction, the treated cellulosic material is washed free of the reactant solution, using tap water. The excess NaOH is removed by addition of glacial acetic acid, or dilute nitric acid, to the wash solution. The washing continues for approximately 5 minutes before the fabric is ironed dry.

The improved wet and dry wrinkle recovery is attained at extremely low degrees of substitution of the cellulose. It is generally preferred to etherify the cellulose to a degree of substitution (D.S.) of between 0.03 and 0.30 to impart the aforementioned properties without significant alteration of the strength, color, appearance, or fibrous form of the cellulosic material.

The washed, etherified cellulose material can be dried, using substantially any of the procedures conventionally employed for drying of cellulosic material. It is preferable to conduct the drying at relatively low temperaturesup to a'temperature of about 110 C.

The following examples are illustrative of certain details of the invention. The 1,4 dihydroxy-2,3 dibromo (or diohloro) butanes used in the examples are white crystalline solids. Meso-1,4 dichloro-2,3 dihydroxybutane was prepared according to United States Patent 2,861,084.

Example 1 Cotton x80 fabric was padded twice with 10% aqueous 1,4 dihydroxy-2,3 dibromobutane to approximately wet pickup. The fabric was dried 5 minutes at C. in a forced-draft oven, and then padded once through 5% NaOH (in absolute ethanol). The fabric was then cured 16 hours at 25 C. in a sealed polyethylene bag. The fabric was washed in tap water, acidified to remove excess base, washed in tap water again, and ironed dry. The sample was equilibrated overnight at room temperatures beto-re final weight and crease angles were determined. The fabric had a 1.35% weight gain, and dry crease angle (Monsanto, warp and fill) of 231, and a Wet crease angle of 245.

Example 2 The process of Example 1, except that 15 aqueous 1,4 dihydroxy- 2,3 dib ro-rno butane and 7.5% NaOH in absolute ethanol were used. The weight. gain was 2. 35%, and crease angles were 261 (dry), and 243 (Wet).

Example 3 A process of Example 1, except that d,l-1,4 dihydroxy- 2,3 dichloro .but-ane (10% aqueous solution) was used in place of the dibromo compound. A 5% NaOH ethanolic solution was employed in the process. The fabric showed a weight gain of 1.0%, and dry and wet crease recovery angles of 232 and 230, respectively.

Example 5 The process of Example 1. except for the use of a [aqueous solution of d,l-1,4 dihydroxy '2,3 dichloro Ibutane as the cross-linking agent to produce a tabri-c showing a Weight gain of 6.1%, and dry and .wet crease recovery angles of 255 and 225, respectively. Here, too, .a 5% NaOH ethanolic solution was employed.

Example 6 The process of Example 5, except that absolute methanol for the 5% NaOH solution was employed as solvent instead of absolute ethanol, and the use of oven cure temperature of 115 C. for a period of 5 minutes, in place of the polyethylene bag cure at 25 C. The finished fabric had a weight gain of 4.2%, and dry and Wet crease recovery angles of 248 and 231 respectively.

Example 7 The process of Example 1, except for the use of meso- 2,3 dichloro-1,4 dihydroxy butane in 10% aqueous solution, and use of oven cure of 125 C. for 5 minutes, the ethanolic solution of NaOH being 5% by Weight. For solubility reasons, padding of the halohydnin is !best performed at 75 C. The weight gain of the final fabric was 0. 8%, and the crease recovery angles were 249 (dry), and 221 wet).

Example 8 The process of Example 2, except for the use of aqueous meso- 1,4 dichloro-2,3 dihydroxy butane as the precursor to produce a fabric having a weight gain of 2.8%, and dry and wet crease recovery angles of 253 and 230, respectively. For solubility reasons, padding of the halohyd-rin is best performed at C. The sodium hydroxide concentration employed here was 7.5% by weight.

We claim:

1. A process for imparting wash-wear characteristics to cotton cellulosic textile materials, which comprises treating said cotton cellulosic textile materials at room temperature with an aqueous solution of a reagent selected from the group consisting of d,l-1,4 dihydroxy-2,3 dibr omo butane; d,-l1,4 diHYdroxy-ZJ dichloro butane; meso-2,3 dihydroxy-:l,4. dichloro butane; and meso-2,3 dichloro-1,4 dihydroxy butane; and subsequently drying, adding alcohol solution of alkaline catalyst, curing, and washing the fabric.

2. The process of claim 1, wherein the curing step is carried out at a temperature of from 25 to C., for time intervals of from 16 hours to 5 m-inutes-the shorter times being employed with the higher temperatures-and the reagent is from 10% to 15% by weight aqueous solution of d, l-l,4 dihydroxy-2,3 dibromo butane and the alkaline catalyst alcoholic solution is 5.0% to 7.5% by weight of NaOH.

3. The process of claim 1, wherein the curing step is carried out at a temperature of from 25 to 125 C., and the reagent is from 10% to 15 by weight aqueous solution of d,l-1,4 dihydroxy-2,3 dichloro butane and the alkaline catalyst alcoholic solution is 5.0% to 7.5% by weight of NaOH.

4. The process of claim 3, wherein the treatment is carried out at a temperature of from 75 to 125 C., and the reagent is from 10% to 15 by Weight aqueous solution of meso-2,3 dihydroxy-IA dichloro butane.

5. The process of claim 4, wherein the treatment is carried out at temperatures of from 75 to 125 C., and the reagent is from 10% to 15 by weight aqueous solutions of meso-2,3-dichloro-1,4 dihydroxy butane.

6. A process for imparting wash-wear characteristics to cotton cellulose textile material, which comprises treating said cellulosic textile materials at room temperature with only one treating solution consisting of an alcoholic solution of 1,4 dihydroxy-2,3 dibromobutane and sodium hydroxide catalyst until Wash-wear properties are produced.

OTHER REFERENCES McKelvey at 211., Journal of Polymer Science, May 1961, pp. 209-230.

J. TRAVIS BROWN, Acting Primary Examiner. H. WOLMAN, Assistant Examiner. 

1. A PROCESS FOR IMPARTING WASH-WEAR CHARACTERISTICS TO COTTON CELLULOSIC TEXTILE MATERIALS WHICH COMPRISES TREATING SAID COTTON CELLULOSIC TEXTILE MATERIALS AT ROOM TEMPERATURE WITH AN AQUEOUS SOLUTION OF A REAGENT SELECTED FROM THE GROUP CONSISTING OF D,1,-1,4 DIHYDROXY-2,3 DIBROMO BUTANE; D,1-1,4 DIHYDROXY-2,3 DICHLORO BUTANE; MESO-2,3 DIHYDROXY-1,4 DICHLORO BUTANE; AND MESO-2,3 DICHLORO-1,4 DIHYDROXY BUTANE; AND SUBSEQUENTLY DRYING, ADDING ALCOHOL SOLUTION OF ALKALINE CATALYST, CURING, AND WASHING THE FABRIC. 